Carboxyester substituted siloxanes



Patented'Nov. 13, 1956 aliphatic and cycloaliphatic acids such as malonic, malic, tartaric, pimelic, azelaic, tetraphenylsuccinic, cyclohexyl- 2,770,632 dicarboxylic, maleic and dimethylfumaric and aromatic dicarboxylic acids such as phthalic, naphthalic, diphenic,

CARBOXYESTER SUBSTITUTED SHOXANES 5 stilbene dicarboxylic, tolane dicarboxylic, dibenzyldicar- Robert L. Merker, Pittsburgh, Pa., assignor to D boxylic and hydroxylated aromatic dicarboxylic acids such Corning Corporation, Midland, Mich., a corporaas hydroxyterephthahc.

tion of Michigan The siloxanes which are employed in the method of this invention are halomethylsiloxanes which contain at No a i gz 1954 least 1 monovalent hydrocarbon radical attached to the silicon. For the purpose of this invention R can be any 12 Claims. (Cl. 260-4481) monovalent hydrocarbon radical such as for example methyl, ethyl, octadecyl, cyclohexyl, vinyl, allyl, cyclohexenyl, phenyl, tolyl, benzyl, and xenyl. The siloxanes This invention relates to siloxanes having carboxy 15 y Contain either 0116 tWO monovalent hydrocarbon functional groups att h d t h ili radicals attached to the silicon and these hydrocarbon It is the object of this invention to prepare novel or- Iadlcals In51y be the safhe dlffel'ehtganosiloxanes which are useful as lubricants, rust inhibi- F halomethylsllohahes y h P p y halo tors and emulsifiers. The compositions are particularly gehatlng the cofrespohdlhg methylslloxanes y y useful for emulsifying siloxane fluids. Another object he Ph p y halogehatlhg the (foflespohdlhg methyl of this invention is to prepare polyfunctional siloxanes halosilahes and theffiaftel' hydfolyzlng h p All whi h can react i h l h i alcohols to f resins alternat ve method is that of halogenating monomethyland whi h a b l d as ddi i f hydrocarbon trlhalosilanes and thereafter reacting the halogenated masubstituted ili fl id terial with a Grignard reagent carrying the monovalent This invention relates to siloxanes of the formula hydrocarbon i l f i l i l t :1 gi l 2 s-n tlal reaction w1 ta e p ace w1th a s1 lCOIl on e a ogen rather than the halogen attached to the methyl radical. 2 The siloxanes of this invention may be copolymerized where R is a divalent hydrocarbon radical or a hydroxylwith hydrocarbon substituted siloxanes or with halogenated divalent hydrocarbon radical, R i a monovalent ated hydrocarbon substituted siloxanes of the formula hydrocarbon radical and n has a value from 1 to 2 inelusive. R mS1O T The above siloxanes are best prepared by reacting a metallic salt (preferably an alkali metal salt) of the for- Whlch R" 15 any monovalent hydrocarbonfadlcal mula MOOCRCOOH (L the acid salt or mono Salt any halogenated monovalent hydrocarbon radical andm f a i li acid) with a h l th l il of the has a value from 1 to 3 lnclusive. The copolymerlzatlon f l may be carried out employing an acid catalyst in the con- XCH2R, Sio ventional manner shown in the art. Such copolymers may contain from .01 to 99.99 mol percent of the silox- 40 anes of this invention, the remainder being the aforesaid in which compounds R, R and n are as above defined. hydrocarbon and halogenated hydrocarbon substituted The reaction may be carried out at any desired temperasiloxanes. These copolymers are useful as lubricants, ture and preferably in the presence of a mutual solvent rust inhibitors and emulsifiers.

such as dimethylformamide. During the reaction it is The following examples are illustrative only and should preferred that the reaction mixture be acidic in order to not be construed as limiting the invention which is propprevent cleavage of the halomethyl groups of the siloxerly set forth in the appended claims.

ane. In general the reaction proceeds best at temperatures ranging from 80 C. up. After the reaction has Example 1 been completed the metal chloride is removed by filtra- 82. f tion or other means and the solvent is then removed to 3 g m the dlsodlum salt of adlp 1c acld 126 4 g o th d f 0 adipic acid, 100 g. of bis-chloromethyltetramethyldisiloxg nets? 1S 3: when l f h d ane were mixed and heated at 200-220 C. for 2 hours.

in :53 f figy ggi y g gi fi gfl if i The product was extracted with benzene and after re- 3 0 1 l 1 acid and the acid itself. In this case there should be at m Va of the so Vent the slloxane havmg the form a least one mol of the acid per mol of the disalt. During W the reaction there will be some polymeric material formed 55 [H000 (OHEMCO O OHZSUZO which results from the reaction of the disalt with two was obtained. There was also obtained a complex polyhalomethylsiloxane molecules. meric material having the formula:

Meg BT62 M09 M82 HOOC (OHmGOOOHrSMOSiOH OOO (OHr)4o0O0H2si].OsioH O0 C (OH2)4OOOH The primary reaction of this invention may be repre- The disodium salt of the siloxane acid sented by the following equation:

M92 HOOCROOOM+(XCH )R',,SiO [Hooowmhoooomsiho T was marge byrgacting the plroduct NalOH. 1? 0.5

, percent y welg t aqueous so ution o t is sa t was ace 3 n+ X 65 on a sheet of cold rolled steel. There was no rusting after 2 8 hours at room temperature. By contrast the same steel For the purpose of this invention any dibasic carboxylhaving a P of Water thereon rusted in 1/2 houric acid in which R is any divalent hydrocarbon radical or Calcium chloride was added to a solution of the salt any hydroxylated divalent hydrocarbon radical can be employed to make the compositions of this invention. (C 2)4OOOCH2SihO Specific examples of acids which are operative herein are whereupon the calcium salt of the disiloxane acid precipitated. This calcium salt was completely soluble in benzene and in phenylmethylpolysiloxane fluids. It was partially soluble in dimethylpolysiloxane fluids. A film of phenylmethylpolysiloxane fluid and dimethylpolysilox- M82 [HO O C (CH2)4CO O CHzSihO were mixed with octamethylcyclotetrasiloxane and with 1.5 g. of. trifluoroacetic acid. The mixture was refluxed with stirring for 2 hours. The resulting product was a copolymer having the formula in which x has a value of at least one.

Enough aqueous KOH was added to convert the acid ended siloxane to the potassium salt. Water was then removed at 100 C. under reduced pressure. The resulting salt was water soluble but gave a clouded solution similar to that of soap. This material was suitable as an emulsifying agent.

Example 3 20 g. of bis-chloromethyltetramethyldisiloxane, 10.2 g. of succinic acid, 16.8 g. of the dipotassium salt of succinic acid, and 20 g. of dimethylforrnamide were mixed and refluxed 1 hour. The resulting product was filtered free of potassium chloride and there was obtained 12.8 g. of this material which corresponds to the theoretical yield. The filtrate was then washed with water to remove dimethylformamide and part of the succinic acid and the remaining material was dissolved in benzene and filtered to remove the remaining succinic acid. The solvent was then removed and there was obtained 25 g. of a water white liquid having a refractive index at 25 C. of 1.4591 and density at 25 C. of 1.11. This product was primarily of the, formula There was also obtained a higher polymeric material similar to that obtained in Example 1.

Example 4 20 g. of bis-chloromethyltetramethyldisiloxane, 17.6 g. of sebacic acid, 24.1.g. of the dipotassium salt of sebacic acid and 20 g. of dimethylformamide were reacted as in Example 2. The product was purified as shown in Example 2 and there was obtained 30.5 g. of a brown waxy solid which in the super cooled state had a refractive index at 25 C. of 1.4625. This material was primarily o the formula together with some higher polymeric material of a structure similar to that of Example 1.

Example 5 M82 [HOOG COOCHzSihO Example 6 A mixture of 20 g. of chloromethylheptam ethylcyclotetrasiloxane, 26.5 g. of adipic acid, 5.8 g. of the disodium salt of adipic acid and 30 g. of dimethylformamide were refluxed. The resulting product was filtered to remove sodium chloride and some gel which formed and the liquid product had a refractive index of 25 C. of 1.4464

and a density at 25 C. of 1.1 and had the following formula: a V

M zs io-sibnzooo ormicoon M ezsi-o siMe, V 7 V a When 1 mol of this cyclic siloxane, 1 mol ofphenylmethylsiloxane and 1 mol of monovinylsiloxane are refluxed in toluene solution with 1 g. of trifiuoroacetic acid,

a copolymer composed of 25 mol percent dimethylsiloxane, 33.3 mol percent phenylmethylsiloxane, 33.3 mol percent monovinylsiloxane and 8.4 mol percent Me 7 HOOO(CHz)4000OH SiO is obtained.

Example 7 e When 2 mols of the monosodium salt of maleic acid is reacted with 1' mol of (C6115): Et;

ClOHzSi OSiOHzCl the acid (C6115): E132 HOOCOH=OHCOQCHzSi 0SiOH2OOOOH=OHOOOH is obtained.

When 1 mol of this disiloxane is heated with 1 mol of chlorophenylmethylsiloxane at 60 C. in the presence of 1 g. of H2804 a copolymer fluid of the average formula 0 r Ph otaioqutz HOOCCH=OHOOOCHzSiO 0 SiCH2OOOOH=CHCOOH is obtained. 7

Example 8 When 2 mols of monosodium malate, 1 mol of bischloromethyltetramethyldisiloxane and 200 ml. of dimethylformamide are refluxed for 2 hours a mixture of the siloxanes HOOCCHOHCH OOO OHzSi 0 and ' lHooooH CHO is obtained.

When this mixture is copolymerized with vinylmethylsiloxane in accordance with the method of Example 2,

a fluid siloxane copolymer of the average formula M02 Mo M o; r HOOCCHOHOHzCOOOHzSl [OSi SiGH2OOC CHOHCHC0OH a is obtained.

hydrocarbon radicals, R is a monovalent hydrocarbon radical and n has an average value from 1 to 2 inclusive.

2. A copolymeric siloxane in which from .01 to 99.99 mol percent of the polymer units are of the formula (HOOCRCOOCHQR SiO where R is selected from the group consisting of divalent hydrocarbon radicals and hydroxylated divalent hydrocarbon radicals, R is a monovalent hydrocarbon radical.

6 and n has a value from 1 to 2 inclusive, the remainder 9. A copolymeric siloxane in accordance with claim 3 of the polymer units in said copolymer being of the in which both R' and R" are methyl radicals. formula R" SiO M8a M02 M82 4 1n 5 H000(OHMCOOOHzSHOSiLOSlOHzOOC(CHQMOOOH 2 in which x has a value of at least one. in which R" is selected from the group consisting of 11. Me monovalent hydrocarbon radicals and halogenated mono- M15i0$10H1000(03940001! valent hydrocarbon radicals and m has an average value from 1 to 3 inclusive. 10 Me A 3. A siloxane in accordance with claim 1 in which R a l is a methyl radicaL 12. A polymenc srloxane of the formula 4. A siloxane in accordance with claim 1 in which R' R]: R], R]: f is a phenyl radicaL HOOOROOOCHzSlfOSlCHjCOORCOOCHISILOSIOOCRCOOH M 15 where R is selected from the group consisting of divalent [HOOCWHINOOOCHISHEZO hydrocarbon radicals and hydroxylated divalent hydro- 6 carbon radicals, R is a monovalent hydrocarbon radical [HOOG(OH:);COOGH1SihO and x has a value of at least 1.

[HOOC(CH:)aCOOCHzS1]a0 20 References Cited in the file of this patent M moocooooomsigo FOREIGN PATENTS 635,733 Great Britain Apr. 12, 1950 

1. A SILOXANE HAVING THE UNIT FORMULA 